The present invention relates to polypropylene having improved long chain branching particularly such polypropylene presents high melt strength, recovery compliance and/or good relaxation time. The polypropylene with improved long chain branching of the present invention is obtained by irradiating polypropylene with a high energy electron beam in the presence of a grafting agent.
Polypropylene resin is used in a variety of different applications. However, polypropylene resin suffers from the problem of having a low melt strength, which restricts the use of polypropylene in a number of applications because the polypropylene is difficult to process. It is known in the art to increase the melt strength of polypropylene, for example by irradiating the polypropylene with an electron beam. It is known that electron beam irradiation significantly modifies the structure of a polypropylene molecule. The irradiation of polypropylene results in chain scission and grafting (or branching) which can occur simultaneously. Up to a certain level of irradiation dose, it is possible to produce from a linear polypropylene molecule having been produced using a Ziegler-Natta catalyst, a modified polymer molecule having free-end long branches, but the properties are not significantly improved.
For example, U.S. Pat. No. 5,554,668 discloses a process for irradiating polypropylene to increase the melt strength thereof. An increase in the melt strength is achieved by decreasing the melt flow rate, otherwise known as the melt index. It is disclosed that a linear propylene polymer material is irradiated with high energy ionising radiation, preferably an electron beam, at a dose rate in the range of from about 1 to 1xc3x97104 Mrads per minute for a period of time sufficient for a substantial amount of chain scission of the linear, propylene polymer molecule to occur but insufficient to cause gelation of the material. Thereafter, the material is maintained for a period of time sufficient but too long for a significant amount of long chain branches to form. Finally, the material is treated to deactivate substantially all free radicals present in the irradiated material. In addition, the specification discloses the use of a very broad range of dose rates i.e. from 1 to 1xc3x97104 Mrads per minute. High dose rates of greater than about 40 Mrad can result in a substantially fully cross-linked structure of the polypropylene. Such a cross-linked structure is difficult to process.
CA-A-2198651 discloses a continuous method for producing polypropylene mixtures of increased stress-crack resistance and melt strength in which a low-energy electron beam accelerator with an energy of from 150 to 300 keV at a radiation dose of 0.05 to 12 Mrads is employed. This process also suffers from the disadvantage that the production rate of the irradiated powder can be somewhat low for commercial acceptance. Moreover, the polypropylene powder to be irradiated must be in the form of very fine particles. The specification discloses that bifunctional, unsaturated monomers can be added before and/or during the irradiation. Such compounds may include divinyl compounds, alkyl compounds, dienes, or mixtures thereof. These bifunctional, unsaturated monomers can be polymerised with the help of free radicals during the irradiation. However, no indication is given on how to proceed to improve the long chain branching of the polypropylene.
EP-A-0520773 discloses an expandable polyolefin resin composition including polypropylene optionally blended with polyethylene. In order to prepare a cross-linked foam, a sheet of expandable resin composition is irradiated with ionising radiation to cross-link the resin. The ionising radiation may include electron rays, at a dose of from 1 to 20 Mrad. It is disclosed that auxiliary cross-linking agents may be employed which include a bifunctional monomer, exemplified by 1,9-nonanediol dimethyacrylate.
U.S. Pat. Nos. 2,948,666 and 5,605,936 disclose processes for producing irradiated polypropylene. The latter specification discloses the production of a high molecular weight, non-linear propylene polymer material characterised by high melt strength by high energy irradiation of a high molecular weight linear propylene polymer. It is disclosed that the ionising radiation for use in the irradiation step may comprise electrons beamed from an electron generator having an accelerating potential of 500 to 4000 kV. For a propylene polymer material without a polymerised diene content, the dose of ionising radiation is from 0.5 to 7 Mrad. For propylene polymer material having a polymerised diene content, the dose is from 0.2 to 2 Mrad. But once again, there is no indication on the long chain branching.
EP-A-0821018 discloses the preparation of cross linkable olefinic polymers which have been subjected to ionising radiation. The specification exemplifies electron beams of relatively low energy and low doses to split polymeric chains in order to graft silane derivatives onto the polymeric chain. The specification does not address the problem of achieving high melt strength of polymers.
EP-A-0519341 discloses the grafting of vinyl monomers on particulate olefin polymers by irradiating the polymer and treating thereafter with a grafting monomer. In an example, polypropylene is irradiated with an electron beam having an energy of 2 MeV and subsequently treated with maleic anhydride as a grafting monomer.
U.S. Pat. No. 5,411,994 discloses the production of graft copolymers of polyolefins in which a mass of olefin polymer particles is irradiated and thereafter the mass is treated with a vinyl monomer in liquid form. The ionising radiation dose is about 1 to 12 Mrad and the ionising radiation preferably comprises electrons beamed from an electron generator having an accelerating potential of 500 to 4000 kV. The polymer is first irradiated and then treated with a grafting agent.
EP-A-0792905 discloses the continuous production of polypropylene mixtures of increased stress crack resistance and melt strength by the action of ionising radiation. The energy of the ionising radiation is from 150 to 300 keV and the radiation dose ranges from 0.05 to 12 Mrad.
The present invention aims to provide polypropylene resins having improved long chain branching as well as improved melt strength. More particularly the branching index of polypropylene of the invention should be lower than 0.7. It is also a goal of the invention to provide a process to prepare polypropylene with substantially increased long chain branching on the polypropylene molecules following the irradiation, while employing relatively low irradiation doses. It is a further aim to produce polypropylene having not only improved long chain branching and improved melt strength, but also improved recovery compliance and relaxation time.
Accordingly, the present invention provides for polypropylene having increased long chain branching particularly having a branching index of lower than 0.7 melt strength. It has been unexpectedly found that such improved long chain branching (LCB) polypropylene may be obtained by irradiating polypropylene with an electron beam having an energy of at least 5 MeV and with a radiation dose of from 5 to 100 kGray in the presence of a grafting agent for forming long chain branches on the polypropylene molecules.
It has also been unexpectedly found that such improved LCB polypropylene may be obtained with high energies owing to the conjoint use of a grafting agent during the irradiation step.
Such improvement has been found and finally measured through the determination of the branching index.
The branching index as mentioned in the present patent application is obtained by the ratio of weight average MW values inferred from rheological measurement at zero shear viscosity and at crossover points as fully described in Polymer Testing 11, 89 (1992) by K. Bernreitner et al.
Preferably, the polypropylene is irradiated at an energy of at least 10 MeV.
The polypropylene may be a homopolymer of propylene or a random or block copolymer of propylene and one or more olefins and/or dienes selected from ethylene and C4 to C10 1-olefins or dienes, which may be linear or branched. The polypropylene homopolymer may be reinforced by rubber particles, for example ethylene-propylene rubber particles, typically in an amount of up to 30 wt %. The polypropylene may be a terpolymer optionally with a diene, for example norbornadiene, as a comonomer.
According to the present invention, the polypropylene to be irradiated is mixed prior to irradiation with the grafting agent which increases the long chain branching of the propylene molecules as a result of the irradiation. The grafting agent is directly incorporated into the propylene molecule during the irradiation step. The grafting agent includes at least one carbon-carbon double bond, and preferably is polyunsaturated, being for example bi, ter or tetra unsaturated. The non-conjugated unsaturated compounds are preferred, although conjugated saturated compounds may be employed. The grafting agent may contain polar groups, such as ester, anhydride, or imide groups and/or non-metallic elements such as silicon, phosphorous and halogen atoms. The grafting agent may be selected from the group consisting of bismaleimide derivatives; mono-, di-, tri-, tetra-acrylate or methacrylate compounds; organosilane compounds of the formula A4xe2x88x92nSiRn where A are identical or different acrylate or methacrylate or vinyl groups, where R are identical or different alkoxy or acetoxy groups and where n is 1, 2, 3 or 4; xcex1,xcex2-unsaturated acids and their anhydride derivatives; non-conjugated dienes such as 1,5-hexadiene, norbornadiene and dicyclopentadiene; dipentene; polybutadiene and copolymers containing polybutadiene blocks; butadiene based polymers and copolymers; polyisoprene and copolymers containing polyisoprene blocks; isoprene based polymers and copolymers; polyethylene; C4-20 xcex1-olefins either linear or branched; styrene or divinylbenzene; ethylene-propylene rubbers and ethylene-propylene-diene rubbers; di-furnane derivatives; ester derivatives of fatty acids; and vinylpolybutadiene.
A particularly preferred grafting agent comprises tetravinyl silane.
The grafting agent employed in accordance with a preferred aspect of the invention results, following irradiation, in polypropylene molecules having some free end terminations, with a cross-link density which is not so high as to reduce the processability of the polymer.
In a further preferred aspect, functional monomers such as maleic anhydride, styrene, acrylic acid, methacrylic acid, 1,4-butanediol diacrylate, or ethylene glycol dimethacrylate may be incorporated into the polypropylene resin. These functional comonomers promote long chain branching of the polypropylene molecules.
In a particularly preferred embodiment of the invention, polypropylene homopolymer in fluff or powder form in an oxygen-free environment is mixed with a grafting agent. Preferably, the grafting agent comprises from 0.01 to 5 wt % of the weight of the polypropylene, more preferably from 0.01 to 1 wt % of the weight of the polypropylene. A particularly preferred grafting agent comprises tetravinyl silane in an amount of from 0.01 to 1 wt % based on the weight of the polypropylene, most particularly from 0.01 to 0.5 wt % based on the weight of the polypropylene.
The polypropylene/grafting agent mixture is thereafter deposited onto a continuously moving conveyor such as an endless belt. The mixture on the conveyor passes under an electron beam generator which irradiates the mixture. The accelerating potential or energy of the electron beam is at least 5 MeV, more preferably from 5 to 100 MeV, still more preferably at least 10 MeV, yet more preferably from 10 to 25 MeV. The power of the electron beam generator is preferably from 50 to 500 kW more preferably for 120 to 250 kW. The radiation dose to which the polypropylene/grafting agent mixture is subjected is preferably from 10 to 100 kGray, preferably around 15 kGray (10 kGray is equivalent to 1 Mrad). The conveyor speed is adjusted in order to achieve the desired dose. Typically, the conveyor speed is from 0.5 to 20 meters/minute, preferably from 1 to 10 meters/minute, more preferably from 2.25 to 8.5 meters/minute.
As a result of the high irradiating potential of the electron beam, not only can the conveyor speed be significantly higher than in the prior art, but also the thickness of the continuously moving bed of polypropylene/grafting agent mixture on the conveyor can be relatively high. Typically, the bed of polypropylene homopolymer and grafting agent has a thickness of up to 20 cm, most particularly from 5 to 10 cm. The bed of polypropylene homopolymer/grafting agent mixture on the conveyor typically has a width of up to about 1 meter. The irradiation is carried out under an inert atmosphere, such as nitrogen.
After irradiation by the electron beam, the polypropylene powder can be annealed and then treated with at least one known antioxidant additive. The annealing temperature may range from 50 to 150xc2x0, more preferably from 80 to 120xc2x0 C. and the annealing time may range from 1 to 60 minutes, more preferably from 5 to 30 minutes. Thereafter the polypropylene is granulated.
In accordance with the invention, the irradiated polypropylene has increased recovery compliance, relaxation time and melt strength. These particular rheological properties provide an outstanding processing behaviour which allows the polypropylene based polymers produced in accordance with the invention to be suitable particularly for producing films, sheets, fibres, pipes, foams, hollow articles, panels and coatings. The irradiated polypropylene also has improved mechanical properties, such as flexural modulus and impact resistance.